EP0755462B1 - Corrosion inhibition and improvement of adhesion characteristics of reinforcing metals - Google Patents

Corrosion inhibition and improvement of adhesion characteristics of reinforcing metals Download PDF

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Publication number
EP0755462B1
EP0755462B1 EP96904249A EP96904249A EP0755462B1 EP 0755462 B1 EP0755462 B1 EP 0755462B1 EP 96904249 A EP96904249 A EP 96904249A EP 96904249 A EP96904249 A EP 96904249A EP 0755462 B1 EP0755462 B1 EP 0755462B1
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EP
European Patent Office
Prior art keywords
metal
concrete
aqueous
metals
improvement
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96904249A
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German (de)
French (fr)
Other versions
EP0755462A1 (en
Inventor
Manfred Akstinat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cement Intellectual Property Ltd CIP
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Cement Intellectual Property Ltd CIP
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Publication of EP0755462A1 publication Critical patent/EP0755462A1/en
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Anticipated expiration legal-status Critical
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the present invention relates to a method for simultaneous Corrosion inhibition and improvement of the bond properties of Reinforcing metals for concrete and the use of such treated reinforcing metals.
  • D1 that is to say US Pat. No. 2,992,131, describes a method for simultaneously inhibiting corrosion and improving the composite properties of reinforcing metals (iron metal) for concrete by means of an Fe, Zn or Mn phosphating (see claims 1 and 3; column 3 , Lines 5 - 22).
  • the phosphated metal can be post-treated with compositions which contain chromates and / or glyoxal (a known corrosion inhibitor) - see claims 3 and 5.
  • a reinforcing iron is initially phosphated.
  • An oil layer is then applied to the metal surface pretreated in this way and dries out after a certain time.
  • the inside of the above-mentioned shell is initially phosphated and then with a soap consisting of an aqueous solution of Na stearate and palmitate, sprayed.
  • the phosphating step according to the invention is known per se Metal phosphate baths, especially in Fe, Zn, Zn / Ca or Mn phosphate baths executed.
  • Chemical accelerators used for this purpose include water-soluble oxidizing agents such as nitrates, chlorates or chromates or organic accelerators such as N-containing compounds, specifically Aniline or pyridine or aromatic carboxylic acids.
  • the phosphating mentioned takes place batchwise or continuously, in baths or spray systems at room temperatures or above.
  • the drying of the Phosphating layer which can be a few tens of ⁇ m, becomes the same subjected to a subsequent surface rinsing according to the invention; this usually happens at room temperature.
  • Aqueous solutions or slurries of reducing and / or passivating compounds especially of nitrites or hydrazine or hydrazine derivatives or hydroxylamine or hydroxylamine derivatives and of chromates.
  • the phosphated and rinsed metal surface is then washed non-aqueous or aqueous metal or non-metal sols and impregnated with a concrete admixture.
  • Shotcrete samples which were treated according to the invention
  • Reinforcing fibers made of steel were reinforced, showed about 4% higher tensile strength compared to normal armored comparative samples; when the samples were sharpened up even after 6 months of outdoor storage, no corrosion on the Steel fibers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The novel process serves simultaneously to inhibit corrosion and to improve adhesion characteristics of reinforcing metals for and in cement systems. It involves surface treatment of the metal parts by Fe-, Ca/Zn, Zn or Mn-phosphatisation and subsequent surface treatment using an aqueous solution or slurry of reducing and/or passivating compounds (such as nitrites, chromates, hydrazine or hydrazine derivatives, hydroxylamine or hydroxylamine derivatives), and/or organic corrosion inhibitors. If necessary, the phosphate layers can undergo subsequent impregnation with non-aqueous or aqueous solutions of other corrosion inhibitors, e.g. vapour phase inhibitor, adhesive promotors, metal-non-metal sols and/or concrete/cement additives.

Description

Die hier befasste Erfindung betrifft ein Verfahren zur gleichzeitigen Korrosionsinhibierung und Verbesserung der Verbundeigenschaften von Armierungsmetallen für Beton sowie die Verwendung von derart behandelten Armierungsmetallen.The present invention relates to a method for simultaneous Corrosion inhibition and improvement of the bond properties of Reinforcing metals for concrete and the use of such treated reinforcing metals.

D1, d.h. die US-A 2 992 131, beschreibt ein Verfahren zur gleichzeitigen Korrosionsinhibierung und Verbesserung der Verbundeigenschaften von Armierungsmetallen (Eisen-Metall) für Beton durch eine Fe-, Zn- oder Mn-Phosphatierung (siehe Ansprüche 1 und 3; Spalte 3, Zeilen 5 - 22). Nach D1 kann das phosphatierte Metall nachbehandelt werden mit Zusammensetzungen, die Chromate und/oder Glyoxal (ein bekannter Korrosionsinhibitor) - siehe Ansprüche 3 und 5 - enthalten.D1, that is to say US Pat. No. 2,992,131, describes a method for simultaneously inhibiting corrosion and improving the composite properties of reinforcing metals (iron metal) for concrete by means of an Fe, Zn or Mn phosphating (see claims 1 and 3; column 3 , Lines 5 - 22). According to D1, the phosphated metal can be post-treated with compositions which contain chromates and / or glyoxal (a known corrosion inhibitor) - see claims 3 and 5.

Gemäss einer der in D2, d.h. in der EP-A 0 285 593, angegebenen Lehren (Spalte 4, Zeilen 42 bis und mit 52) wird ein Armierungseisen vorerst phosphatiert. Anschliessend wird auf der derart vorbehandelten Metall-Oberfläche eine Oelschicht aufgebracht, welche nach einer gewissen Zeit austrocknet.According to one of the teachings given in D2, ie in EP-A 0 285 593 (column 4, lines 42 to and with 52), a reinforcing iron is initially phosphated. An oil layer is then applied to the metal surface pretreated in this way and dries out after a certain time.

D3, d.h. die EP-A 0 095 413, schliesslich beansprucht eine Wickel-Hülle für ein Vorspann-Drahtseil in vorgespannten Beton-Werkstücken. D3, ie EP-A 0 095 413, finally claims a winding sleeve for a prestressing wire rope in prestressed concrete workpieces.

Die Innenseite der genannten Hülle wird vorerst phosphatiert und anschliessend mit einer Seife, bestehend aus einer wässerigen Lösung von Na-Stearat und -Palmitat, besprüht.The inside of the above-mentioned shell is initially phosphated and then with a soap consisting of an aqueous solution of Na stearate and palmitate, sprayed.

Das erfindungsgemässe Verfahren zur gleichzeitigen Korrosionsinhibierung und Verbesserung der Verbundeigenschaften von Armierungsmetallen für Beton ist demgegenüber in den weiter unten folgenden Patentansprüchen gekennzeichnet.The inventive method for simultaneous corrosion inhibition and improving the composite properties of reinforcing metals for concrete, on the other hand, is given in the following Characterized claims.

Der erfindungsgemässe Phosphatierungs-Schritt wird in an sich bekannten Metallphosphatbädern, v.a. in Fe-, Zn-, Zn/Ca- oder Mn-Phosphatbädern ausgeführt. Hierzu eingesetzte chemische Beschleuniger umfassen wasserlösliche Oxydationsmittel wie Nitrate, Chlorate oder Chromate bzw. organische Beschleuniger wie N-haltige Verbindungen, speziell Anilin oder Pyridin oder aromatische Carbonsäuren.The phosphating step according to the invention is known per se Metal phosphate baths, especially in Fe, Zn, Zn / Ca or Mn phosphate baths executed. Chemical accelerators used for this purpose include water-soluble oxidizing agents such as nitrates, chlorates or chromates or organic accelerators such as N-containing compounds, specifically Aniline or pyridine or aromatic carboxylic acids.

Die genannte Phosphatierung geschieht batchweise oder kontinuierlich, in Bädern oder Spritzanlagen bei Raumtemperaturen oder darüber.The phosphating mentioned takes place batchwise or continuously, in baths or spray systems at room temperatures or above.

Nach der üblicherweise mittels Heissluft ausgeführten Austrocknung der Phosphatierungsschicht, die einige 10 um betragen kann, wird dieselbe erfindungsgemäss einer anschliessenden Oberflächenspülung unterworfen; diese geschieht normalerweise bei Raumtemperatur.After the drying of the Phosphating layer, which can be a few tens of µm, becomes the same subjected to a subsequent surface rinsing according to the invention; this usually happens at room temperature.

Verwendet werden hierzu wässerige Lösungen bzw. Aufschlämmungen von reduzierenden und/oder passivierenden Verbindungen, v.a. von Nitriten oder Hydrazin bzw. Hydrazinderivaten oder Hydroxylamin bzw. Hydroxylaminderivaten und von Chromaten.Aqueous solutions or slurries of reducing and / or passivating compounds, especially of nitrites or hydrazine or hydrazine derivatives or hydroxylamine or hydroxylamine derivatives and of chromates.

Anschliessend wird die phosphatierte und gespülte Metalloberfläche mit nichtwässerigen oder wässerigen Metall- oder Nichtmetallsolen und einem Beton-Zusatzmittel imprägniert. The phosphated and rinsed metal surface is then washed non-aqueous or aqueous metal or non-metal sols and impregnated with a concrete admixture.

Es wurde festgestellt, dass erfindungsgemäss behandelte Armierungsmetalle schon während des Lagerns - auch im Freien - ein deutlich geringeres Korrosionsbild ergeben als nicht behandelte Proben.It was found that reinforcing metals treated according to the invention even during storage - even outdoors - a clear one result in less corrosion than untreated samples.

Spritzbeton-Proben, welche mit erfindungsgemäss behandelten Armierungsfasern aus Stahl (Länge 2 bzw. 4 cm) verstärkt waren, zeigten eine um etwa 4 % höhere Zugfestigkeit verglichen mit normal armierten Vergleichsproben; beim Aufspitzen der Proben zeigten sich auch nach 6-monatiger Aussenlagerung keine Korrosionsansätze an den Stahlfasern.Shotcrete samples, which were treated according to the invention Reinforcing fibers made of steel (length 2 or 4 cm) were reinforced, showed about 4% higher tensile strength compared to normal armored comparative samples; when the samples were sharpened up even after 6 months of outdoor storage, no corrosion on the Steel fibers.

Claims (4)

  1. Method for the simultaneous prevention of corrosion and improvement of the bonding properties of reinforcement metals for concrete, characterised in that after a surface treatment of the metal parts by means of phosphatising with Fe, Ca/Zn, Zn or Mn the phosphatised metal surface is then washed with an aqueous solution or slurry of reducing and/or passivating compounds, and then impregnated with non-aqueous or aqueous metal or non-metal sols and a concrete additive.
  2. Method according to claim 1, further characterised in that the aqueous solution or slurry contains nitrites or hydrazine.
  3. Use of the method according to claim 1 or 2 on rods, plates, nails, wires, pens, support files, fibres or differently designed metal parts, the surfaces of which are made of iron or iron alloys, zinc or zinc alloys and/or other phosphatisable metals.
  4. Use of the reinforcement metals obtained according to claim 1 in concrete bearing or support components and industrial floors and ceiling elements and in the form of metal fibres in gunned concrete, wherein the improvement of the bond between the reinforcement and the concrete also leads to an increase in the mechanical strength of all parts.
EP96904249A 1995-04-13 1996-03-19 Corrosion inhibition and improvement of adhesion characteristics of reinforcing metals Expired - Lifetime EP0755462B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH01080/95A CH689307A5 (en) 1995-04-13 1995-04-13 Process for both corrosion inhibition and strengthening the bonding properties of reinforcing metals.
CH108095 1995-04-13
CH1080/95 1995-04-13
PCT/IB1996/000244 WO1996032522A1 (en) 1995-04-13 1996-03-19 Corrosion inhibition and improvement of adhesion characteristics of reinforcing metals

Publications (2)

Publication Number Publication Date
EP0755462A1 EP0755462A1 (en) 1997-01-29
EP0755462B1 true EP0755462B1 (en) 1999-08-18

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EP96904249A Expired - Lifetime EP0755462B1 (en) 1995-04-13 1996-03-19 Corrosion inhibition and improvement of adhesion characteristics of reinforcing metals

Country Status (7)

Country Link
EP (1) EP0755462B1 (en)
JP (1) JPH10501849A (en)
AT (1) ATE183553T1 (en)
CH (1) CH689307A5 (en)
DE (1) DE59602778D1 (en)
DK (1) DK0755462T3 (en)
WO (1) WO1996032522A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100245851B1 (en) * 1997-01-16 2000-03-02 한규택 Gluing method of gluing, anti-rust paints for steel pipe and steel bar
JP2001271184A (en) * 2000-03-24 2001-10-02 Nisshin Kako Kk Corrosion protection treating agent and method for stainless steel
WO2011076273A1 (en) * 2009-12-23 2011-06-30 Vsl International Ag Improved strand and method of producing the same
JP5312526B2 (en) * 2011-06-13 2013-10-09 株式会社ピーエス三菱 Method for inhibiting corrosion of PC tendons
CN103161182A (en) * 2011-12-09 2013-06-19 彭道儒 Novel anticorrosion process of concrete reinforcing steel bar phosphorization mitigation method
CN104962935A (en) * 2015-06-13 2015-10-07 周彩球 Copper alloy acid pickling passivant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2992131A (en) * 1957-03-21 1961-07-11 Jenolite Ltd Treatment of metal surfaces
FR2527246A1 (en) * 1982-05-21 1983-11-25 Freyssinet Int Stup IMPROVEMENTS IN PRE-STRESS CONDUITS AND THEIR MANUFACTURING METHODS
BE1000432A6 (en) * 1987-04-03 1988-12-06 Centre Rech Metallurgique Method for improving the corrosion resistance of steel rebar and self-quenching income.

Also Published As

Publication number Publication date
DE59602778D1 (en) 1999-09-23
JPH10501849A (en) 1998-02-17
EP0755462A1 (en) 1997-01-29
WO1996032522A1 (en) 1996-10-17
DK0755462T3 (en) 2000-03-13
ATE183553T1 (en) 1999-09-15
CH689307A5 (en) 1999-02-15

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